Detergent additive composition

ABSTRACT

A detergent additive composition containing a water-insoluble surfactant or surfactant mixture is disclosed. The insoluble surfactant from the additive composition enhances the detergency of the conventional detergent product with which it is used more than it would be increased if a soluble surfactant were used in the additive composition; this composition allows the use of less toxic surfactants. A method for cleaning textiles including treating textiles with this composition in combination with a conventional detergent product is also disclosed.

United States Patent 1 1 Winston 1541 DETERGENT ADDITIVE COMPOSITION [75] Inventor: Anthony E. B. Winston, Liverpool,

[73] Assignee: Church & Dwight Co., Inc.,

Syracuse, NY.

[22] Filed: Dec. 13, 1974 [21] Appl. No; 532,527

Related US. Application Data [63] Continuation-in-part of Ser. No. 352,078, April 17,

1973, abandoned,

[52] US. CI. 252/89; 252/540, 252/559 [51] lnt. CI. CllI) l/OO [58] Field Of Search 252/89, 540,559, DIG. I

[56] References Cited UNITED STATES PATENTS 2,746,932 5/1956 Vitale 252/540 2,956,025 10/1960 Lew 252/559 3,625,909 12/1971 Berg et a1. .1 252/559 3,626,559 12/1971 Rossmann cl a1... 252/540 3,649,569 3/1972 McCarty 252/543 3,679,608 7/1972 Aubert et a1 v 252/540 X 3,697,451 10/1972 Mausnev et almi 252/559 X 3,720,621 3/1973 Smeets 252/540 X 1 Dec. 9, 1975 FOREIGN PATENTS OR APPLICATIONS 785,655 10/1957 United Kingdom 252/540 1,118,297 6/1968 United Kingdom OTHER PUBLICATIONS Schick, Nonionic Surfactants, V01. 2, 605-608.

pp. 479-et al., Surface Active Agents, etc., Vol. II, 1958, pp. 479-480.

Primary ExaminerWilliam E. Schulz Attorney, Agent, or Firm-Hammond & Littell [57] ABSTRACT 9 Claims, No Drawings DETERGENT ADDITIVE COMPOSITION REFERENCETO A PRIOR APPLICATION This application is a continuation-in-part of my copending, application Ser. No. 352,078, filed Apr. 17, 1973 and now abandoned.

THE PRIOR ART Although the idea of optimizing the hydrophobiclipophilic balance (HLB) of the surfactant system in the range of 13 to 15 is will known, few laundry detergents currently available utilize this knowledge. Most laundry detergents are based on the sole use of anionic surfactants or these materials together with small quantities of the higher ethoxylated nonionics. Sometimes small amounts of soaps are added as foam control agents and sometimes small amounts of alkanolamides are added as foam boosters. Generally this is done for economic processing, and product stability reasons. The cheapest surfactants available are the alkylbenzene sulfonates and although they provide acceptable detergency they cannot be easily employed for I-ILB adjustment. The most suitable anionic surfactants for detergents are generally too hydrophilic for optimum detergency. However, these anionic materials are readily spray dried with other detergent builders and fillers into free flowing powders. The resulting products, containing reasonable levels of alkylbenzene sulfonates have no special tendency to cake on storage and since the surfactants are dry, the products have no tendency to bleed. On the other hand, nonionic surfactants and detergent alcohols, which are especially amenable for adjusting the HLB of detergent formulations are relatively expensive. Nonionics, especially those with low HLB numbers are also particularly difficult to spray dry since they plume and pollute the atmosphere. Since most nonionic surfactants are liquids they can also cause caking problems and give products with a tendency to bleed. Also it has sometimes been found that nonionic based detergents are more irritating, particularly to the eyes, than anionic formulations. Thus most formulations are based primarily on anionic surfactants and if some level of nonionic surfactant is included in the formulation, the more hydrophilic higher ethoxylated alcohols and phenols are used. Therefore, most laundry detergents do not provide the maximum possible detergency for the level of surfactants used and higher detergency could be obtained by lowering the HLB of the surfactant system.

Sometimes it is desirable to use an additive product with the laundry detergent. For example, it is necessary to use bleach additive products together with a regular laundry detergent to remove ink, ketchup and other stains. It is also desirable to use a water softening or conditioning additive with the laundry detergent to improve the performance of the detergent in extra hard water. Although most of the presently marketed detergent additives perform their desired subordinate function reasonably well, e. g. of bleaching, water softening, etc. many of these products actually lower the detergency of the laundry detergent with which they are used.

It is thus desirable to improve additive products and their surfactant systems so that they not only perform their specifically required function, but also so that they improve the general detergency of the laundry product with which they are used.

The use of water-soluble surfactants in additives is conventional; however, water-insoluble surfactant systems have not been used.

Water-insoluble surfactants are mentioned in British Pat. No. l ,1 18,297 although the final mixture of surfactants is soluble. Also only nonionic surfactants are mentioned in this patent and the patent specifically requires the use of dialkylphenol-ethylene oxide adducts. Also the patent refers to detergents and not detergent additive products. In addition, British Pat. No. 1,0 I 8,940 describes the use of ethoxylated partial glyerides of C to C fatty acids in cosmetic preparations for hair and skin care. However its use as an additive in connection with detergents is not contemplated.

The incorporation of higher aliphatic alcohols into detergent fonnulations to boost foam levels and increase detergency is also described in US. Pat. Nos. 2,,746,932; 2,956,025 and British Pat. No. 785,655. However, these patents refer to detergents and not to detergent additive products. Also the final formulations are water soluble. The use of long alkyl chain anionic, zwitterionic and nonionic surfactants in detergent formulations for the purpose of fabric softening is mentioned in US. Pat. No. 3,649,569 although no mention of increased detergency or soil removal is mentioned. Also again no mention of detergent additive products are mentioned.

OBJECTS OF THE INVENTION An object of the present invention is the development of a detergent additive composition which improves the detergency of the detergent product with which it is used.

Another object of the invention is the development of a detergent additive composition containing 1 from 0. l% to 60% by weight of a water insoluble surfactant system consisting essentially of either (a) an essentially water-insoluble nonionic, anionic or amphoteric surfactant having a lipophilic moiety with from 8 to 24 carbon atoms and at least one polar nonionic, anionic or amphoteric moiety or (b) a mixture of a watermiscible nonionic, anionic or amphoteric surfactant with a water-insoluble nonionic, anionic or amphoteric surfactant such that the final mixture is water-insoluble, where the said water-insoluble surfactant system has an HLB value between 2 and l l, and (2) from 40% to 99.9% of other detergency builder salts, detergent fillers, bleaching agents and their stabilizers and activators, enzymes or other materials required depending on the end use of the detergent additive product.

it is a further object of the present invention to provide a method for washing soiled articles of laundry textiles, comprising treating the said soiled article to be washed with an aqueous solution containing (i) 0.2 to 25 grams/liter of solution of a conventional detergent product together with (ii) 0.05 to 25 grams per liter of solution of a detergent additive composition containing (1) from 0.] to 60% by weight of a water-insoluble surfactant system consisting essentially of (a) an essentially water-insoluble nonionic, anionic or amphoteric surfactant having a lipophilic moiety with from 8 to 24 carbon atoms and at least one polar nonionic, anionic or amphoteric moiety or (b) a mixture of water-soluble nonionic, anionic or am photen'c surfactants with a water-insoluble nonionic, anionic or amphoteric surfactant such that the final mixture is water-insoluble and (2) from 40 to 99.9% of other detergency builders salts, detergent fillers, bleaching agents and their stabilizers and activators, enzymes or other materials required depending on the desired properties of the detergent additive product, such that the HLB value of the total surfactant system added to the wash liquor from the detergent and additive product is adjusted to be closer to its optimum value for the removal of the particular soils and the cleaning of the particular substrates.

These and further object of the present invention will become apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION This invention relates to a detergent additive composition containing (1) from 0.1% to 60% by weight of a water-insoluble surfactant system consisting essentially of either (a) an essentially water-insoluble nonionic, anionic or amphoteric surfactant having a lipophilic moiety with from 8 to 24 carbon atoms and at least one polar nonionic, anionic or amphoteric moiety or (b) a mixture of a water-soluble nonionic, anionic or amphoteric surfactant with a water-insoluble nonionic, anionic or amphoteric surfactant such that the final mixture is water-insoluble, where the said water-insoluble surfactant system has an I-[LB value between 2 and l l and (2) from 40% to 99.9% of other detergency builders salts, detergent fillers, bleaching agents and their stabilizers and activators, enzymes or other materials required depending on the end use of the detergent additive product, as well as the method of washing soiled articles using the detergent additive composition of the invention together with another conventional detergent product.

More particularly, the invention relates to a detergent additive composition consisting essentially of 1) from 0.1% to 60% by weight of a water-insoluble surfactant system selected from the group consisting of (a) an essentially water-insoluble component having a lipophilic moiety with from 8 to 24 carbon atoms and at least one polar moiety, selected from the group consisting of anionic surface-active agents, nonionic surfaceactive agents and amphoteric surface-active agents, where said water-insoluble surfactant system has an HLB value between 2 and ll, and (2) from 40% to 99.9% of at least one customary detergent additive selected from the group consisting of builder salts, detergent fillers, bleaching agents and their stabilizers and activators, enzymes, corrosion inhibitors, buffers, antiredepositing agents, optical brighteners, foam stabilizers and foam inhibitors.

An essentially water-insoluble, surfactant component is a compound which has a lipophilic moiety with from 8 to 24 carbon atoms and at least one polar nonionic, anionic or amphoteric moiety. The lipophilic moiety is advantageously a primary or secondary alkyl, an alkenyl, an alkylphenyl, an alkenylphenyl or an alkylnaphthyl group. A polar nonionic moiety is advantageously a hydroxyl, an ether, a polyether hydroxyl, an amine oxide, an amide or an ester group or groups. A polar anionic moiety is advantageously a sulfonate, sulfate, or carboxylate group or groups. An amphoteric moiety contains both anionic and cationic centers, generally sulfonates, sulfates or carboxylates with primary, secondary, tertiary or quaternary ammonium groupings. For convenience, the essentially water-insoluble component will be referred to as a water-insoluble surfac tant. In the detergent additive compositions of the invention, the water-insoluble surfactant lowers the hydrophilic-lipophilic balance (HLB) of the detergent products with which it is used, to a more optimum value for the soils being removed or the substrate being cleaned, while still remaining sufficiently soluble in aqueous wash liquors to solubilize the surfactants and the soils. The detergent additive composition of the invention is thus more effective and can allow the use of less toxic material in its composition and in the final washing liquors.

A surfactant is water-soluble if it forms a clear solution in water at its temperature and concentration of usage. If the surfactant forms a cloudy dispersion or it is immiscible with water at its temperature and concentration of usage, it is water-insoluble.

The detergent additive composition generally comprises of 0.1% to 60%, preferably from 0.5% to 20%, more particularly from l% to 10%, and most particularly from 1% to 5% by weight of the water-insoluble surfactant system and from 40% to 99.9%, preferably from to 99.5%, more particularly from to 99% and most particularly from to 99% by weight of the additive ingredient. The detergent additive composition is usually applied in the form of an aqueous solution containing from 0.05 to 25 grams/liter, preferably from 0.5 to 2.5 grams/liter of the additive compositions, together with 0.2 to 25 grams per liter, preferably 0.5 to 10 grams/liter of another conventional detergent product.

The invention therefore also is directed to a method for washing soiled articles of laundry and textiles, comprising treating the said soiled article to be washed with an aqueous solution containing (i) 0.2 to 25 grams/liter of solution of a conventional detergent product together with (ii) 0.05 to 25 grams/liter of solution of a detergent additive composition containing 1) from 0.1 to 60% by weight of a water-insoluble surfactant system consisting essentially of (a) an essentially water-insoluble nonionic, anionic or amphoteric surfactant having a lipophilic moiety with from 8 to 24 carbon atoms and at least one polar nonionic, anionic or amphoteric moiety or (b) a mixture of water-soluble nonionic, anionic or amphoteric surfactant with a water-insoluble nonionic, anionic or amphoteric surfactant, such that the final mixture is water-insoluble, where the said water-insoluble surfactant system has an I-[LB value between 2 and 11, and (2) from 40% to 99.9% by weight of at least one additive ingredient.

The invention is also directed to an improvement in the method of washing soiled articles of laundry and textiles, comprising treating the said soiled article to be washed with an aqueous solution containing (i) 0.2 to 25 grams/liter of solution of a conventional detergent product together with (ii) from 0.05 to 25 grams/liter of solution of a detergent additive composition containing conventional additive ingredients. The said improvement relates to the addition of from 0.1% to 60% by weight of said additive composition of a waterinsoluble surfactant system consisting essentially of (a) an essentially water-insoluble nonionic, anionic or amphoteric surfactant having a lipophilic moiety with from 8 to 24 carbon atoms and at least one polar nonionic, anionic or amphoteric moiety or (b) a mixture of water-soluble nonionic, anionic or amphoteric surfactant with a water-insoluble nonionic, anionic or amphoteric surfactant, such that the final mixture is waterinsoluble, where the said water-insoluble surfactant system has an HLB value between 2 and l l, to said additive composition.

For optimum detergency on ordinary soils the HLB value of the surfactant mixture from the additive composition and detergent product should be between and 13. However, particularly oily or greasy soils require a lower HLB. Also the optimum HLB value for detergency varies with the type of fabric or surface being washed. Thus surfactant mixtures of additive and detergent outside this range of HLB are also included in the invention.

The level and type of surfactant used in the product is dependent on the final end use of the product. Generally, the surfactant level and type would be chosen so as to produce maximum detergency with most of the conventional detergents to which it is to be added or to best remove the particular type of soil for the removal of which the additive product was designed.

It has been found that, when using a conventional detergent product, the increased detergency obtained with the detergent additive composition of the invention over that obtained using only a conventional detergent product alone, is not dependent on the pH as long as the pH is neutral to alkaline. The increased detergency of the total surfactant system does, however, vary slightly with the temperature of the wash liquors since the HLB of surfactants is different at different temperatures. For example, many of the ethoxylated nonionics become more insoluble as the temperature increases. Therefore, the term water-insoluble or water-soluble" is always at the usage temperature of the wash liquors. The water-insoluble surfactant present in the detergent additive composition increases the detergency of the detergent product with which it is used more than the detergency would be increased if a water-soluble surfactant were used in the detergent additive composition or increases the ability of the detergent to remove a particular soil for the removal of which the additive product was designed.

A surface-active agent is a material which, when added to a solution, modifies the surface properties of that solution. Usually, these materials consist of molecules composed of hydrophobic hydrocarbon groups, containing between 8 and 24, preferably 10 and carbon atoms (though this can be more or less) and one or more polar groups.

Modification of the surface properties of the solution is accomplished by orientation of the surfactant molecules at the solution interfaces. In the case of water solutions, the molecules become oriented such that the hydrophobic groups are directed away from the solution and the polar groups are oriented towards the solution.

If the polar group of the surfactant is strongly hydrophilic, it enables the surfactant to solubilize by forming micelles. These micelles are aggregates of surfactant molecules oriented such that the hydrophobic portions of the molecules are towards the center of the micelle. e hydrophilic groups thus form a soluble surface around the outside of the micelle. lf the polar group o the surfactant is only weakly hydrophilic, the surfactant cannot be solubilized in this way. However, if a more hydrophilic surfactant is added to the less soluble surfactants, mixed micelles can be formed and the insoluble surfactant can be solubilized.

Sodium dodecylbenzene sulfonate and decaethoxypentadecanol are examples of anionic and nonionic water-soluble surfactants, while triethoxypentadecanol and sorbitan mono-oleate are examples of waterlnsoluble nonionic surfactants. The long chain primary alcohols or secondary alcohols and esters of long chain fatty acids are not known as surfactants since alone they are completely immiscible in water. Nevertheless, since these materials possess one or more hydrophobic hydrocarbon groups and possess some degree of polarity, they tend somewhat to become oriented at the solution surface, and can be solubilized by more hydrophilic surfactants. Thus, these materials may be utilized as surfactants in mixtures with a strongly hydrophilic surfactant.

Generally laundry detergents are formulated with surfactant systems which have too high an HLB for optimum detergency or for the removal of particularly oily stains. This is due to economic, stability and toxicity factors as explained above.

in wash liquors, the effect of mixing water-insoluble surfactants with water-soluble surfactants is to lower the hydrophilic-lipophilic balance of the wash system. Thus if the amount of water-insoluble surfactant added in the detergent additive composition is not excessive, the addition of the additive results is increased detergency and makes the composition more penetrating to sebum, oily soil and grease stains, while still remaining soluble enough to solubilize the soils.

As well as carrying out its subordinate function, the use of an additive composition containing a waterinsoluble surfactant system, together with a conventional detergent containing a water-soluble surfactant system has two positive results. The detergency of the total system, as explained above may be increased or the detergent system may become more penetrating to the particular soils being removed while less toxic materials can be incorporated into the additive formulation.

The addition of lower HLB surfactants into detergent additive compositions is easily accomplished. Generally relatively low levels of these materials are required and the materials can be added by dry blending rather than spray drying so that pluming is not a problem. Also since the usage levels are low the addition of these materials results in only a moderate increase in formulation costs. For the same reason, even when liquid surfactants are used, bleeding of the material from the product is not a problem, providing the substrate is reasonably absorbant.

The surfactant system in the detergent additive com position is comprised of water-insoluble nonionic, anionic or amphoteric surfactants or mixtures thereof, or mixtures of water-soluble anionic, nonionic or amphoteric surfactants with water-insoluble anionic, nonionic or amphoteric surfactants such that the mixed surfactant system is water-insoluble.

The combination of the above water-insoluble surfactant system of the detergent additive with the watersoluble surfactant system of the detergent product, with which it is used, results in increased detergency. Also less toxic surfactants, in contrast to the conventional ethoxylated alcohols, ethoxylated alkylphenols, alkylbenzene sulfonates, etc. can be substituted in the detergent additive formulation while still providing increased detergency.

Examples of suitable detergent additive products which are applicable to the addition of the waterinsoluble surfactant system of this invention are a chlorine bleach, a dry safety bleach, a water softener or conditioner. However, this invention is not restricted to these additives and may incorporate the water-insoluble surfactant system with wash alkalis. The additives can be used with any conventional laundry detergent.

Preferred detergent additive compositions have the following formulation:

0.5% to 20% by weight of the water-insoluble surfactant system defined above.

50% to 99.5% by weight of solid, finely-divided wash alkalis, inorganic builder salts or inorganic washinert water-soluble salts.

% to 35% by weight of bleach ingredients of the chlorine bleach type (hypochlorites and chlorites) or the peroxide bleach type (inorganic peroxyhydrates) together with stabilizers and activators.

0% to by weight of other additive materials of the type of enzymes, optical brighteners, antiredepositing agents, corrosion inhibitors, foam stabilizers and foam inhibitors.

The level and type of surfactant used in the product is dependent on the final end use of the product. Generally, the surfactant level and type would be chosen so as to produce maximum detergency with most of the conventional detergents to which it is to be added or to best remove the particular soil for the removal of which the detergent additive is designed.

Examples of suitable water-insoluble nonionic surfactants are the water-insoluble ethylene oxide adducts of primary or secondary, branched or straight chain, alkanols or alkenols containing 8 to carbon atoms in the alcohol chain and an average of between 1 and 6 mols of ethylene oxide.

Also suitable are the water-insoluble ethylene oxide adducts of branched or straight chain, alkylor alkenylphenols containing between 8 to 12 carbon atqs in the alkyl or alkenyl chain, and between l to 6 mols of ethylene oxide.

Also suitable are the water-insoluble propylene oxide adducts of the above primary or secondary, branched or straight chain, alcohols or alkylphenols; also, the water-insoluble ethylene oxide-propylene oxide mixed adducts of the above branched or straight chain, alcohols or alkylphenols.

Water-insoluble nonionic surfactants which also have some cationic properties are suitable. Examples of these materials are the ethoxylated alkylamines, for example (diethoxylated) aminoalkanes having 8 to 2] carbon atoms in the alkyl chain, and containing from i to 6 mols of ethylene oxide.

As explained above, although not generally known as surfactants, unethoxylated primary or secondary alcohols, such as alkanols and alkenols, containing 8 to 20 carbon atoms, may be used as water-insoluble nonionic surfactants. Also the esters, for example lower alkyl esters such as methyl and ethyl esters of long chain fatty acids of 8 to 24 carbon atoms, or esters of long chain fatty alcohols of 8 to 24 carbon atoms acylated with lower alkanoic acids such as acetic acid may be used. The above alcohols and esters are particularly useful in that they have low toxicity. Thus when these materials are incorporated into the detergent additive the resulting products are especially non-irritating.

Also suitable are the fatty acid diethanolamine condensates having form 8 to 24 carbon atoms in the acyl group, such as N,N-(diethanol)-alkanoic acid amides having from 8 to 24 carbon atoms in the acyl group.

Also suitable as an essentially water-insoluble nonionic component having a lipophilic moiety with from 8 to 24 carbon atoms and a polar nonionic moiety, or the water-insoluble nonionic surfactant, are water-insoluble partial or whole esters and ethers of fatty acids or fatty alcohols with 8 to 24 carbon atoms with alkanepolyols and cycloalkanepolyols such as the sugar alcohols, glucose or sucrose, pentaerythitol, glycerol, etc.; water-insoluble alkylamine oxides having 8 to 24 carbon atoms in the alkyl chain; and water-insoluble ethoxylated fatty acids and fatty acid amides where the fatty acids have from 8 to 24 carbon atoms, and the acids and amides are ethoxylated with l to 7 ethylene oxide units.

A suitable water-insoluble anionic surfactant is obtained from the longer primary or secondary, branched or straight alkyl or alkenyl sulfonates or sulfates containing 18 to 28 carbon atoms in the alkyl or alkenyl chain.

Also suitable water-insoluble anionic surfactants are obtained from the longer straight or branched chain alkylphenyl or alkenylphenyl sulfonates or sulfates containing 15 to 20 carbon atoms in the alkyl or alkenyl chain.

The anionic surfactants are mostly present as salts of the alkali metals, particularly of sodium or potassium, as well as the ammonium salts and salts of lower alkylamines or lower alkylolamines such as triethanolamine.

Amphoteric surfactants contain in the molecule both acidic groups, such as carboxyl, sulfonic acid, sulfuric acid half esters, phosphonic acid and phosphoric acid partial esters groups, and also basic groups, such as primary, secondary, tertiary and quaternary ammonium groups. Amphoteric compounds with quaternary ammonium groups belong to the type of the betaines.

Examples of suitable water-insoluble amphoteric surfactants include alkali metal sulfonimidazoline hydrox ides, for example, l-(2'-hydroxy ethyl)-l-(2'-hydroxy- 3-sodium sulfo-propyl)-2-longer chain alkyl-imidazoline hydroxides of 16 to 28 carbon atoms in the alkyl chain. Also suitable are the alkyl betaines of more than 16 carbon atoms in the alkyl chain of the formula where R is an alkyl group with 16 to 28 carbon atoms.

The water-insoluble surfactants used may also be mixtures of water-soluble surfactants with waterinsoluble surfactants providing that the final mixture is water-insoluble.

Suitable water-soluble nonionics for this purpose are the water-soluble ethylene oxide adducts of primary or secondary, branched or straight chain, alkanols or alkenols containing 8 to 20 carbon atoms in the alcohol chain and more than 7 mols of ethylene oxide. Also suitable as water-soluble nonionics are the water-soluble ethylene oxide adducts of alkylor alkenyl-phenols containing 8 to 12 carbon atoms in the alkyl or alkenyl chain, and more than 7 mols of ethylene oxide.

Also suitable are the water-soluble, propylene oxideethylene oxide mixed adducts of the above alkylor alkenyl-phenols or the primary or secondary alcohols, as well as the water-soluble amine oxides such as the water-soluble higher-alkyl-di-lower alkyl-amine oxides, and the water-soluble ethoxylated higher alkylamines having 8 to 24 carbon atoms in the alkyl and from 5 to 30 ethylene oxide units. In addition, the water-soluble partial esters or ethers of higher fatty acids or higher fatty alcohols with alkanepolyols, water-soluble poly- 9 hydroxy detergent alcohols, and water-soluble ethoxylated higher fatty acids and higher fatty acid amides can be utilized.

The water-soluble anionic surfactants are those ordinarily used in the art. Preferred are the synthetic anionic surfactants of the sulfonate and sulfate types.

The sulfonates include, for example, alkylbenzenesulfonates with preferably straight-chain C especially C, alkyl residues, alkanesulfonates, obtainable from preferably saturated aliphatic C especially C hydrocarbons by sulfochlorination or sulfoxidation, mixtures of alkenesulfonates, hydroxyalkanesulfonates and alkanedisulfonates, known as *olefinsulfonates", which are formed by acidic or alkaline hydrolysis of the sulfonation products which first result from terminal or non-terminal C and preferably C 12.18 olefins by sulfonation with sulfur trioxide. The sulfonates, utlizable according to the invention, include also salts, preferably alkali metal salts of a-sulfo fatty acids and salts of esters of these acids with mono or polyhydric alcohols with l to 4, and preferably 1 to 2 carbon atoms.

Further useful sulfonates are salts of fatty acid esters of hydroxyethanesulfonic acid or of dihydroxypropanesulfonic acid, the salts of the fatty alcohol esters of lower aliphatic or aromatic sulfomonoor dicarboxylic acids, containing 1 to 8 carbon atoms, the alkylglycerylether sulfonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.

Surfactants of the sulfate type include fatty alcohol sulfates, especially those derived from coconut fatty alcohols, tallow fatty alcohols or from oleyl alcohol, also sulfatized fatty acid alkylamides or fatty acid monoglycerides and sulfated alkoxylation products of alkylphenols (C alkyl), fatty alcohols, fatty acid amides, or fatty acid alkylolamides with 0.5 to 20, preferably 1 to 8, and particularly 2 to 4 ethylene and/or propyleneglycol residues in the molecule.

As anionic surfactants of the carboxylate type, for example, the fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids, are suitable as well as the amide-like condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, such as glyco coll, sarcosine or with protein hydrolysates when they are water-soluble.

The anionic surfactants are mostly present as salts of the alkali metals, particularly of sodium or potassium, as well as the ammonium salts and salts of lower alkylamines or lower alkylolamines such as triethanolamine.

Examples of suitable water-soluble amphoteric surfactants include alkali metal sulfo-imidazoline hydroxides, for example, l-(2'-hydroxy ethyl )-l-(2'-hydroxy- 3-sodium sulfo-propyl)-2-alkyl-imidazoline hydroxides of 7 to carbon atoms in the alkyl chain. Also suitable are the alkyl betaines of more than 6 carbon atoms in the alkyl chain of the formula where R is an alkyl group with 6 to 22 carbon atoms.

The waterinsoluble surfactant for these mixtures are 10 commercial plants or in the household, using both washing machines and washing by hand.

Other materials should be incorporated into the additive composition, depending on the desired end use of the product. Examples of such materials might be corrosion inhibitors such as the silicates, for example alkali metal silicates; buffering agents such as bicarbonates or borates, for example alkali metal bicarbonates or alkali metal borates; anti-redeposition agents such as sodium carboxymethyl cellulose, polyvinyl alcohol or polyvinyl pyrrolidone', peroxide bleaching agents such as percarbonates, perborates or persulfates, for example of alkali metals; together with their stabilizers such as magnesium silicates and activators, such as poly N-acyl or O-acyl compounds; chlorine bleaching agents such as the alkali metal hypochlorites and chlorites; optical brighteners such as derivatives of aminostilbenesulfonic acid, or of diaminostilbenedisulfonic acid, or of diarylpyrazolines, or of carbostyrils; and also enzymes for stain, particularly protein stain removal, usually designed as proteases.

The enzyme preparations to be used are mostly a mixture of enzymes with different effects, such as proteases, carbohydrases, estereases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases, or nucleases. Of particular interest are the enzymes, obtained from bacteria strains or from fungi, such as Bacillus subtilis or Streptomyces griseus, particularly proteases and amylases, which are relatively stable towards alkalis, percompounds, and anionic surfactants and are still effective at temperatures up to C.

Fillers may also be incorporated into the formulation. Examples of suitable materials might be the alkali metal sulfates or chlorides, or water.

Foam boosters such as the alkanolamides can also be used in the formulations providing that the total surfactant in the composition is still water-insoluble.

The following examples are merely illustrative of the present invention without being deemed limitative in any manner thereof.

COMPOSITION 1 Dry Safety Bleach COMPOSITION 2 Liquid Detergency Booster and Water Conditioner Range Filler Base in in L'l Insoluble Surfactant 0 15.0 Solvent e.g. Tridecyl Benzene 0 50,0 Sodium Citrate 0 30.0 20.0 Tetra Sodium Pyrophosphate 0 10.0 Sodium Xylene Sulfonute 0 10.0 O tical Brighteners 0 2.0 0.3 C C. PVA 0 2.0 Water 0 90,0 7 l .7

Examples of specific water-insoluble surfactants or ABLE ll water-insoluble surfactant mixtures which are suitable P I h 1 h l dd Designation l'll'flflfy ilCU -Et CUB OXl C i1 UCl for the above comp osit ons are given below in Table I wnh [2 to '5 Carbon moms in although this invention is not restricted to these surfacalcohol chain and an average of 9 mols of ethylene oxide. S-l tants. Each surfactant is numbered, and these numbers Ody] phenobethylem oxide adduc Wm] are used in the exam; les which follow: an average of 12 to 13 mols of ethylene oxide S-Z Sodium salt of dodecyl benzene sulfonate 8-3 Tallow amine ethylene oxide adduct with an average of mols of ethylene oxide 5-4 TABLE I Designation Primary alcoholethylene oxide adduct with l2 to 15 carbon atoms in alcohol EXAMPLES 1 TO 6 an average 3 of 15 Standard soil swatches (cotton, cotton/dacron 35/65 and durable press cloths from Testfabrics, lnc. and cotton EMPA 101 cloth) were washed in the Terg-o-tom- 0 tyl ph n lthy oxide adduct w t an eter" at 55C in 120 ppm hard water for 12 minutes at average 3 N2 100 RPM. Subsequently, the cloths were rinsed for 5 minutes in warm tap water. After drying, the soil re- Mmure or primary acnhol containing [2 m moved from the cloths was compared by measuring the 13 carbon atoms and sodium salt or increase 1n reflectance on a reflectometer. l5 grams of dodecyl heme sulfmate cloth were used per liter of wash solution. The concenof l7 parts alcohol to 3 parts sulfon ate N 3M tratlon of detergent used and the type and concentration of the additive composition added is shown in the table of results.

cowamne'elhylele oxde adduc "F The results shown in the Table III give a comparison average of 2 mols of ethylene oxtde N4 Mixture of ethoxylated primary alcohols with Of th detergency obtained using detergent alone, the

13 f f detergent plus additive composition containing insolu- 3 mols of ethylene oxide and a similar b1 rt. d h d I dd. alcohol with an average of 7 mols of I e 3 actalltior f d an t e etergent P us a Ethylene Oxide in the ratio of 111 ttve composition containing a comparable water-soluble surfactant.

Commercial products A, B and C are phosphate W p adduc 5 based laundry detergents. Commercial product D is a mols of ethylene oxide N-6 non-phosphate carbonate based product.

TABLE III lnsoluble Soluble Total Example Surfactant Surfactant Increase ln No. Product ln Additive ln Additive Reflectance 1 Commercial Product A 1.5 gm/l 80.5 Commercial Product A 1.5 gm/l with B-l 1.5 m/i N-l 875 Commercial Product A 1.5 gm/I with B! l.5 gm/l 5-1 80.0 2 Commercial Product B 1.35 gm/l 80.5 Commercial Product B 1.35 gm/l with B-l 1.5 gm/l N 2 97.5 Commercial Product B 1.35 gm/l with at 1.5 gm/l 5-2 79.5 3 Commercial Product C 1.35 gm/l 765 Commercial Product C 1.35 gm/l with B-l 1.5 gm/l N-3 9 10 Commercial Product C 1.35 gm/l with B-l 1.5 m," 3 84.5 4 Commercial Product D I25 gm/l 965 Commercial Product D 1.35 gm/l with B-l 1.5 gmi'l N4 1025 Commercial Product D 1.25 m}! with 13 1 1.5 gm/l i s4 90.5 5 Commercial Product A I.5 gm/l with L-I 2.0 gmfl N-S 36.0 Commercial Product A 1.5 gm/l with L-l 2.0 mii S-l 74.0 6 Commercial Product C 1.35 gm/l with L\ 2.0 grn/l N76 1105 Commercial Product C L gm/l with L-] 2.0 gm/l 572 6915 Examples of specific soluble surfactants which are Table lll shows the increased detergency obtained utilized for comparison purposes are given below in using a conventional laundry detergent, together with Table ll. Each surfactant is numbered, and these numadditive compositions of the invention (containing wabers are used in the examples which follow. ter-insoluble surfactant systems) over the detergency obtained using the laundry detergent alone or with an additive composition containing water-soluble surfactants. The conventional laundry detergents used with additive compositions of the invention show, in Table III, a substantial increase in reflectance (indicating an increase in detergency) as compared to the detergent used alone. The conventional laundry detergents used with additive compositions containing soluble surfactants show no increased reflectance as compared to the detergent used alone.

Although the present invention has been disclosed in connection with a few preferred embodiments thereof, variations and modifications may be resorted to by those skilled in the art without departing from the principles of the new invention. All of these variations and modifications are considered to be within the true spirit and scope of the present invention as disclosed in the foregoing description and defined by the appended claims.

I claim:

1. A detergent additive composition consisting essentially of (1) from 0.1% to 60% by weight of a waterinsoluble surfactant system selected from the group consisting of (a) an essentially water-insoluble component having a lipophilic moiety with from 8 to 24 carbon atoms and at least one polar moiety selected from the group consisting of nonionic, anionic and amphoteric, and b) an essentially waterinsoluble mixture of said component (a) with a water-soluble surfactant selected from the group consisting of anionic surface-active agents, nonionic surface-active agents and amphoteric surface-active agents, where said water-insoluble surfactant system has an HLB value between 2 and l l, (2) from 40% to 99.9% by weight of at least one detergent salt selected from the group consisting of builder salts, detergent fillers and buffer, (3) from to 35% by weight of bleaching agents and their stabilizers and activators, and (4) from 0 to 5% by weight of at least one customary detergent additive selected from the group consisting of enzymes, corrosion inhibitors, antiredepositing agents, optical brighteners, foam stabilizers and foam inhibitors.

2. The detergent composition of claim 1 wherein at least one polar nonionic moiety of said essentially water-insoluble nonionic component is selected from the group consisting of hydroxyl, ether, polyether hydroxyl, amine oxide, amides and ester groups.

3. The detergent additive composition of claim 1 wherein component l is present in an amount of from 0.5% to by weight and component (2) is present in an amount of from 80% to 99.5% by weight.

4. The detergent additive composition of claim 3 wherein component (3) is present in an amount of from 20% to 35% by weight.

5. The detergent additive composition of claim 3 wherein component (4) is present in an amount of from 0.05% to 3% by weight.

6. The detergent additive composition of claim 1 wherein component l is present in an amount of from I% to l0% by weight and component (2) is present in an amount of from 90% to 99% by weight.

7. The detergent composition of claim 3 in which the water-insoluble nonionic surfactant is selected from the group consisting of an ethylene oxide adduct of an alkanol or an alkenol having 8 to 20 carbon atoms in the alkanol or alkenol chain and containing 1 to 6 mols of ethylene oxide, an ethylene oxide adduct of an alkylphenol or alkenylphenol having from 8 to l2 carbon atoms in the alkyl or alkenyl chain and containing from 1 to 6 mols of ethylene oxide, a propylene oxide adduct of an alkanol or alkenol having 8 to 20 carbon atoms in the alkanol or alkenol chain and containing 1 to 6 mols of propylene oxide, a propylene oxide adduct of an alkylphenol or an alkenylphenol having 8 to 12 carbon atoms in the alkyl or alkenyl chain and containing from I to 6 mols of propylene oxide, an ethylene oxide-propylene oxide mixed adduct of an alkanol or an alkenol having 8 to 20 carbon atoms, and containing from I to 6 mols of ethylene oxide and from I to 6 mols of propylene oxide, an ethylene oxide-propylene oxide mixed adduct of an alkylphenol or an alkenylphenol having from 8 to 12 carbon atoms in the alkyl or alkenyl chain and containing from 1 to 6 mols of ethylene oxide and from 1 to 6 mols of propylene oxide, ethoxylated alkylamines or alkenylamines having 8 to 24 carbon atoms in the alkyl or alkenyl chain and containing from I to 6 mols of ethylene oxide, alkanols and alkenols having from 8 to 24 carbon atoms, esters of long chain fatty acids of 8 to 24 carbon atoms with lower alkanols, esters of long chain fatty alcohols of 8 to 24 carbon atoms acylated with lower alkanoic acids, and N,N-diethanol fatty acid amides having from 8 to 24 carbon atoms in the fatty acid group.

8. A method for washing soiled articles of laundry and textiles, comprising treating said soiled articles to be washed with an aqueous solution containing from 0.2 to 25 grams/liter of solution of a conventional detergent composition containing watersoluble surfactants and from 0.2 to 25 grams/liter of solution of a detergent additive composition consisting essentially of (1) from 0.1% to 60% by weight of a water-insoluble surfactant system selected from the group consisting of (a) an essentially water-insoluble component having a lipophilic moiety with from 8 to 24 carbon atoms and at least one polar moiety selected from the group consisting of nonionic, anionic and amphoteric, and (b) an essentially water-insoluble mixture of said component (a) with a water-soluble surfactant selected from the group consisting of anionic surface-active agents, nonionic surface-active agents and amphoteric surface-active agents, where said water-insoluble surfactant system has an HLB value between 2 and l l, (2) from 40% to 99.9% by weight of at least one detergent salt selected from the group consisting of builder salts, detergent fillers, and buffers, (3) from 0 to 35% by weight of bleaching agents and their stabilizers and activators, and (4) from 0% to 5% by weight of at least one customary detergent additive selected from the group consisting of enzymes, corrosion inhibitors, anti-redepositing agents, optical brighteners, foam stabilizers and foam inhibitors, where the total system has an HLB value between 10 and 13.

9. In the method of washing soiled articles of laundry and textiles comprising treating said soiled articles to be washed with an aqueous solution containing from 0.2 to 25 grams/liter of solution of a conventional detergent composition containing water-soluble surfactants and from 0.2 to 25 grams/liter of solution of a conventional detergent additive composition containing at least one customary detergent additive selected from the group consisting of builder salts, detergent fillers, bleaching agents and their stabilizers and activators, enzymes, corrosion inhibitors, buffers, antiredepositing agents, optical brighteners, foam stabilizers and foam inhibitors, the improvement consisting of employing from 0.1% to 60% by weight of a water- 16 lected from the group consisting of anionic surface-active agents, nonionic su rface-active agents and amphoteric surface-active agents, where said water-insoluble surfactant system has an HLB value between 2 and l l, in said detergent additive composition, whereby the total system has an HLB value of between 10 and I3. i i

Disclaimer 3,925,224.Anth0ny E. B. Winston, Liverpool, N .Y. DETERGENT ADDI- TIVE COMPOSITION. Patent dated Dec. 9, 1975. Disclaimer filed Oct. 14, 1976, by the assignee, Chum/z, d5 Dwight 00., Inc.

Hereby enters this disclaimer to claims 1 t0 7 of said patent.

[Oficz'al Gazette December 14, 1.976.] 

1. A DETERGENT ADDITIVE COMPOSITION CONSISTING ESSENTIALLY OF (1) FROM 0.1% TO 60% BY WEIGHT OF WATER-INSOLUBLE SURFACTANT SYSTEM SELECTED FROM THE GROUP CONSISTING OF (A) AN ESSENTIALLY WATER-INSOLUBLE COMPONENT HAVING A LIPOPHILIC MOIETY WITH FROM 8 TO 24 CARBON ATOMS AND AT LEAST ONE POLAR MOIETY SELECTED FROM THE GROUP CONSISTING OF NONIONIC, ANIONIC AND AMPHOTERIC, AND (B) AN ESSENTIALLY WATER-INSOLUBLE MIXTURE OF SAID COMPONENT (A) WITH A WATER-INSOLUBLE SURFACTANT SELECTED FROM THE GROUP CONSISTING OF ANIONIC SURFACE-ACTIVE AGENTS, NONIONIC SURFACE-ACTIVE AGENTS AND AMPHOTERIC SURFACE-ACTIVE AGENTS, WHERE SAID WATER-INSOLUBLE SURFACTANT SYSTEM HAS AN HLB VALUE BETWEEN 2 AND 11, (2) FROM 40% TO 99.9% BY WEIGHT OF AT LEAST ONE DETERGENT FI
 2. The detergent composition of claim 1 wherein at least one polar nonionic moiety of said essentially water-insoluble nonionic component is selected from the group consisting of hydroxyl, ether, polyether hydroxyl, amine oxide, amides and ester groups.
 3. The detergent additive composition of claim 1 wherein component (1) is present in an amount of from 0.5% to 20% by weight and component (2) is present in an amount of from 80% to 99.5% by weight.
 4. The detergent additive composition of claim 3 wherein component (3) is present in an amount of from 20% to 35% by weight.
 5. The detergent additive composition of claim 3 wherein component (4) is present in an amount of from 0.05% to 3% by weight.
 6. The detergent additive composition of claim 1 wherein component (1) is present in an amount of from 1% to 10% by weight and component (2) is present in an amount of from 90% to 99% by weight.
 7. The detergent composition of claim 3 in which the water-insoluble nonionic surfactant is selected from the group consisting of an ethylene oxide adduct of an alkanol or an alkenol having 8 to 20 carbon atoms in the alkanol or alkenol chain and containing 1 to 6 mols of ethylene oxide, an ethylene oxide adduct of an alkylphenol or alkenylphenol having from 8 to 12 carbon atoms in the alkyl or alkenyl chain and containing from 1 to 6 mols of ethylene oxide, a propylene oxide adduct of an alkanol or alkenol having 8 to 20 carbon atoms in the alkanol or alkenol chain and containing 1 to 6 mols of propylene oxide, a propylene oxide adduct of an alkylphenol or an alkenylphenol having 8 to 12 carbon atoms in the alkyl or alkenyl chain and containing from 1 to 6 mols of propylene oxide, an ethylene oxide-propylene oxide mixed adduct of an alkanol or an alkenol having 8 to 20 carbon atoms, and containing from 1 to 6 mols of ethylene oxide and from 1 to 6 mols of propylene oxide, an ethylene oxide-propylene oxide mixed adduct of an alkylphenol or an alkenylphenol having from 8 to 12 carbon atoms in the alkyl or alkenyl chain and containing from 1 to 6 mols of ethylene oxide and from 1 to 6 mols of propylene oxide, ethoxylated alkylamines or alkenylamines having 8 to 24 carbon atoms in the alkyl or alkenyl chain and containing from 1 to 6 mols of ethylene oxide, alkanols and alkenols having from 8 to 24 carbon atoms, esters of long chain fatty acids of 8 to 24 carbon atoms with lower alkanols, esters of long chain fatty alcohols of 8 to 24 carbon atoms acylated with lower alkanoic acids, and N,N-diethanol fatty acid amides having from 8 to 24 carbon atoms in the fatty acid group.
 8. A method for washing soiled articles of laundry and textiles, comprising treating said soiled articles to be washed with an aqueous solution containing from 0.2 to 25 grams/liter of solution of a conventional detergent composition containing water-soluble surfactants and from 0.2 to 25 grams/liter of solution of a detergent additive composition consisting essentially of (1) from 0.1% to 60% by weight of a water-insoluble surfactant system selected from the group consisting of (a) an essentially water-insoluble component having a lipophilic moiety with from 8 to 24 carbon atoms and at least one polar moiety selected from the group consisting of nonionic, anionic and amphoteric, and (b) an essentially water-insoluble mixture of said component (a) with a water-soluble surfactant selected from the group consisting of anionic surface-active agents, nonionic surface-active agents and amphoteric surface-active agents, where said water-insoluble surfactant system has an HLB Value between 2 and 11, (2) from 40% to 99.9% by weight of at least one detergent salt selected from the group consisting of builder salts, detergent fillers, and buffers, (3) from 0 to 35% by weight of bleaching agents and their stabilizers and activators, and (4) from 0% to 5% by weight of at least one customary detergent additive selected from the group consisting of enzymes, corrosion inhibitors, anti-redepositing agents, optical brighteners, foam stabilizers and foam inhibitors, where the total system has an HLB value between 10 and
 13. 9. In the method of washing soiled articles of laundry and textiles comprising treating said soiled articles to be washed with an aqueous solution containing from 0.2 to 25 grams/liter of solution of a conventional detergent composition containing water-soluble surfactants and from 0.2 to 25 grams/liter of solution of a conventional detergent additive composition containing at least one customary detergent additive selected from the group consisting of builder salts, detergent fillers, bleaching agents and their stabilizers and activators, enzymes, corrosion inhibitors, buffers, anti-redepositing agents, optical brighteners, foam stabilizers and foam inhibitors, the improvement consisting of employing from 0.1% to 60% by weight of a water-insoluble surfactant system selected from the group consisting of (a) an essentially water-insoluble component having a lipophilic moiety with from 8 to 24 carbon atoms and at least one polar moiety selected from the group consisting of nonionic, anionic and amphoteric, and (b) an essentially water-insoluble mixture of said component (a) with a water-soluble surfactant selected from the group consisting of anionic surface-active agents, nonionic surface-active agents and amphoteric surface-active agents, where said water-insoluble surfactant system has an HLB value between 2 and 11, in said detergent additive composition, whereby the total system has an HLB value of between 10 and
 13. 